Reactive Nitrogen Monitoring

Reactive Nitrogen Monitoring

Some definitions NOy NO + NO 2 + NO 3 + 2xN2 2 O 5 + HNO 3 + HONO + HO 2 NO 2 + RONO 2 (organic nitrates such as PAN and alkyl nitrates) + RONO (organic nitrites) + NO 3 - (particulate nitrate). The ecology community defines Total Reactive Nitrogen to include N 2 O which is not reactive in the sense considered here, thus we define Total Chemically Reactive Nitrogen to exclude N 2 O and N 2.

NEEDS Ecosystem health Total deposition estimates (wet and dry) of all sulfur and reactive nitrogen species Critical loads Attribution of each species to its emission source (control measures) Other effects of these species (visibility, health )

Issues Deposition is not measured but estimated from limited wind measurements. Some key species are not measured Accuracy with which some species are measured Time scale of measurement 1 week Need shorter sampling time increment for credible source apportionment (preferable hourly but not >24 hr.

Species of interest Dry Species (Current) SO 2 /SO 4 HNO 3 /NO 3 NH 4 Dry Species (Missing) NH 3 Reduced organic gases (Aliphatic amines..) NO x (NO and NO 2 ) Oxidized organic gases (PAN - alkyl nitrates ) Reduced and oxidized organic nitrogen containing particulates.

Accuracy/Uncertainty SO 2 /SO 4 measured reasonable well for both wet and dry Nitrogen is problematic across the board Cut point is ill defined (coarse vs fine) HNO 3 /NO 3 split has large error NH 4 error (underestimated) may be on order of 20-50%

A typical dry deposition budget? Total Deposition Budget (Spring) GAS CONCENTRATION BUDGET 10% 4% 7% 9% 1% 3% 20% 20% wet ON wet no3 wet nh4 hno3 nh3 nox ON Gas no3 nh4 ON Gas 27% NOx 7% NO3 1% NH4 5% HNO3 26% 26% NH3 34%

Modified IMPROVE

Urban Comparison of 3 NH 3 Techniques

Outline Motivation CASTNET Overview Sampling Setups of the Major Networks Proposed Sampling Trains for CASTNET and the Chemical Speciation Network Features of SASS Denuder Prototype 1 SASS Testing: Experimental Design Results: Blanks, Collection Efficiency, Total Load Capacity Conclusions: Prototype 1 Features of SASS Denuder Prototype 2 Results: Blanks and Collection Efficiency Conclusions: Prototype 2

Developing and Testing Prototype Compact Denuders for Ambient Air Sampling Applications Misha Schurman (1), Jeffrey L. Collett, Jr. (1), Susanne V. Hering (2), Derek E. Day (3), William C. Malm (3), Brian Lee (4): (1) Department of Atmospheric Science, Colorado State University, Fort Collins, CO; (2) Aerosol Dynamics Inc., Berkeley, CA; (3) Cooperative Institute for Research in the Atmosphere (CIRA)/National Park Service, Colorado State University; (4) USEPA, Washington, DC

Dry gas and particle ON Can get get estimates of oxidized ON both in gas and particle phase using catalytic converters and NO x boxes on a near real time basis

Trace Gas Samplers (off the shelf and custom)

Online N measurements: Two 3 Channel Instruments NO y analyzer DIRECT 1. NO Y (inlet moly 285C) 2. NO Y (denuded inlet) 3. NO Y (filtered inlet) BY DIFFERENCE 1. Total 2. HNO 3 3. pno 3 +HNO 3 NH 3 analyzer 1. Total Gas Phase Nitrogen (moly 815C) 2. Traditional NO x (moly 315C) 3. NO 1. NH 3 2. NO 2

Low NO : not a locally driven event Winter Overnight NO y Event pno 3 +HNO 3 HNO 3 Dominated by NO y plus smaller contributions of NH 3 and particulate NO 3 -

Questions Are current procedures for estimating dry deposition meaningful? (high time resolution met data combined with 1 wk average concentrations measurements) What needs to be measured that isn t currently being measured? Is split between various species important SO 2 /SO 4, HNO 3 /NO 3, NH 3 /NH 4, etc or is total sulfur, or total gas/particle phase reactive nitrogen adequate? For ecosystem response may not be so important? For attribution and model assessment it is critical! Can defensible critical loads be set without a knowledge of total nitrogen? What sampling frequency/duration is acceptable both in time and space?

Some Possible Changes Eliminate met monitoring if it isn t being used for other purposes. At a minimum add an impregnated filter to the existing filter pack to measure NH 3. Replace current filter pack with similar filter pack (including NH 3 ) that operates automatically for time intervals of Everyday or Every third day. Add NH 3 and HNO 3 to the IMPROVE system. Measure total ON gas/particles at some sites. Speciate ON at some basic level

2007 2008 Notes: Average 2007 and 2008 annual NO 2 from SCIAMACHY satellite. The factor on colorbar is 1.0E+14 molecules per cm 2. The resolution of the data is 0.125 deg x 0.125 deg. Each pixel contain the median of monthly data.

Notes: The ratio of average NO2 for year 2008 to the year 2007 (i.e. NO 2 _ year2008 / NO 2 _ year2008 ) annual NO 2 from SCIAMACHY satellite. The low NO 2 concentration data (NO 2 < 10 15 ) are not considered here. The resolution of the data is 0.125 x 0.125. Each pixel is derived from the median of 2007 and 2007 months data.

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Other Recommendations from EPA NOX/SOX review We recommend monitoring a suite of reactive nitrogen species the sum of which is Total Chemically Reactive Nitrogen defined as the sum of all oxidized species except N 2 O and the sum of ammonia and ammonium. Total Chemically Reactive Nitrogen = NOy + NHx Species Method NOy (total oxidized nitrogen) Reduction to NO followed by chemiluminescence NO - 3 (particulate nitrate) Denuder/filter sampling followed by ion chromatography HNO3 (nitric acid vapor) Filter/denuder and followed by ion chromatography. NH3 (ammonia) Filter/denuder followed by colorimetry or ion chromatography NH4+ (ammonium) Denuder/filter followed by colorimetry or ion chromatography

WHAT WE REALLY NEED TO MEASURE WET GAS PARTICLE Temporal scale (gas/particle) SO 2 /SO 4-2 ***** **** ***** Min/hr/day/week NO 2 /HNO 3 - /NO 3 - **** ****(***CASTNET) ****(***CASTNET) Min/hr/day/week NH 3 /NH 4 - *** *** *** Min/hr/day/week Total ON *** * * Integrated sample/event based ON r * (markers) ON o * (markers) ON b * (markers) * * (markers) *** *** Min/hr/day/week (gas/part) Event for markers ** * Integrated samples? ***** Measure with high degree of accuracy **** Measure with reasonable accuracy *** Measure with low accuracy ** Research monitoring * Currently cannot do Note: measurements should be event based for wet deposition and gases and particles measured at least on a 24 hr schedule.

Next Steps Establish/examine need for ON measurements at x number of sites? Develop denuders to do NH 3, NH 4, and HNO 3 /NO 3 split (within 6 months year) Test filter based measurements for gas/particle phase oxidized ON measurements (1+ years) Develop marker technology/methodology for apportioning ON in wet deposition (2+ years?) Do the same for reduced gas/particles (time?) Implementation schedule (Funding??)

Nitrogen Monitoring Wet ON at a number of regionally representative sites Develop method for apportioning wet ON to reduced, oxidized, biological NHx at a number of regionally representative sites NOy at a number regionally representative sites How to measure total reduced ON gas and/or particle phase? Supplemental measurements in ROMO east/west additional species temporally representative

Wet DON Can measure TON Can t directly measure reduced, oxidized, or biological ON important to make these distinctions from an apportionment perspective because sources are distinctive Can use receptor type models to apportion DON if one has reliable chemical markers Measure reduced OC markers such as amines and urea for reduced DOC Measure oxidized OC markers such as alkyl nitrates, nitrophenols, and other nitroaromatic Measure biological markers such as amino acids and peptides Apply simple regression models or more sophisticated models such as PMF and UNMIX.

How important is AON? 51 studies in North America have DON at 38±19% of TON (Wet) As much as 30% of particulate OC is nitrogen containing Gas % of TON?

What isn t measured? NH 3 Organic nitrogen either in wet or dry (gas and particle phase) or its reduced, oxidized or biological forms NO 2, peroxyacetyl nitrate (PAN) and related alkyl nitrates Aliphatic amines Proteins, amino acids, etc

Tabular summary Species NOy (total oxidized nitrogen) NO 3- (particulate nitrate) HNO 3 (nitric acid vapor) NH 3 (ammonia) NH + 4 (ammonium) Method Reduction to NO followed by chemiluminescence Denuder/filter sampling followed by ion chromatography Filter/denuder and followed by ion chromatography. Filter/denuder followed by colorimetry or ion chromatography Denuder/filter followed by colorimetry or ion chromatography WHAT S MISSING: ORGANIC NITROGEN